Resinous product and process of making same



Patented May 14, 1935 Q 1 mzsmoos raonoo'r AND raoonss or MAKING SAME Joseph V. Meigs, Hastings upon Hudson, N.

assignor to Plastix Corporation, Wilmington, Del., acorporationwof Delaware No Drawing. Original application January 15,

1927, Serial No. 161,468. Divided and this application July 14, 1932, Serial No. 622,458

2 Claims. (01- 260-2) This invention relates to improved resinous retoughness. This is quite contrary to what would action products derived from carbohydrates, be expected. suitable for commercial'use in .the manufacture The use of such increased proportions of hexa of molding compositions; molded articles, lamiwould be expected to result in mechanical weak- 5 nated material prepared by hot pressing impregness rather than strength, and to give rise to 5 nated or coated sheets of fibrous material, difiiculties in hot-pressing and molding, since it varnishes, etc., all as will be hereinafter more is known that hexa normally evolves ammonia fully described and claimed. in reacting with phenols or resins of the phenol- Resinous reaction products of carbohydrates formaldehyde types. The evolution of a large and phenols are well known. Such resinous proportion of ammonia would naturally be re- 10 products may be produced by heating the cargarded as liable to cause blistering and porosity. bohydrate with a phenol in thepresence of a Nevertheless, I have been able to successfully catalyst. They will be fusible or infusible, acmold a carbohydrate-phenolic resinous product cording to the conditions under which they are wherein the proportion of hexa amounted to as made. If fusible, they may be rendered infusimuch as 30 per cent of the weight of the resin, 11* bleby suitable heating, particularly in the preswithout difilculty, and have been able to remove ence of hardening agents. the product from the hot mold without resorting One of the common methods of utilizing such to cooling, the resulting product being free from resins consists in employing them as binding blisters.

agents for fibrous, cellular or other suitable ma- I have found that ammonia reacts with carbo- 20 terial in the preparation of molded or pressed hydrate-phenol resins. This offers apossible exarticles for use in the electrical or mechanical planation for the capacity of such resins to react arts and in this case the fibrous or other material with large proportions of hexa as described, wit acts as supporting and extending material for the results mentioned.

the resin. In their final form such products In order to attainthe mechanical strength and 25 should for commercial purposes, possess a high toughness desirable in commercial molded or degree of resistance to water, heat, mechanical pressed objects of the type herein described, I stresses and shocks and electrical influences, i. e;, employ more than 10 per cent of hard nin agent. the final product should be as inertas possible preferably hexamethylene tetramine, based on the so and possess a high degree of mechanical strength weight of carbohydrate-phenol resins used. In and toughness. I employing such increased proportions, I may use One of the objects of the present invention is them in conjunction th any f t e yt provide a resinous body of t type mentioned, (irate-phenol resins of the prior art but I prefer to possessing, in comparison with products h t employ resins prepared as described in my Umted fore produced an increased degree of re i tance States Patent 1,593,342, issued July 20, 1926, and 35 t mechanical strains or Shocks. Another in my copending application Serial No. 92,640, ject is. to minimize the capacity of such products March 1926' 13363315933 r absorbing water and to render them less which the present application ism parta continsusceptible in other respects to the action of nation Assta'ted theremihe greater the propor- 40 water. tion of phenol combined with the carbohydate or 40 Hexamethyhne tetramine (often referred to derivatwes thereof, the greater is the strength of the resulting resins when hardened with hexa. as hexa) will react with carbohydrate-phenolic d render them fusible. Lhave to d The application of the hardening agent to the resin and the utilization of the resulting potenthat carbohydrate-phenolic resinous products many reactive resinous body may be brought prepared with the customary proportions of 'th an well known method. hexamethylene tetrarmne are relatively weak aboutm accordance W Y In carr in out the invention in its referred from the standpoint of mechanical strength and y g p form I employ a carbohydrate resin which is toughness transverse breakmg strength and either fusible, i. e.; capable of melting to a liqthe impact or shock resistance are relatively low. uid consistency, or at least capable of yielding to I have found however, that by using an pressure when heated. The less the viscosityv of creased Proportion of hexa, in e cases as the resin when heated the greater is the ease with much as 20 per cent or more, based on the weight which it may be molded or pressed under heat of resin, I can prepare products possessing a and pressure, as for example when used as a 65 greatly increased mechanical strength and binder for comminuted filling or supporting material or when employed to impregnate or coat supporting material in sheet form, e. g., woven or felted fabric.

I then incorporate in the resin and hardening agent a filling or supporting material by any known method to secure a composition which when pressed and heated will yield hard, strong, tough coherent masses. During the molding or pressing operation, the fusibility and plasticity of the composition decrease, under the influence of heat, so that the final product is comparatively infusible and thermorigid. The term heat-set may be applied to such a composition, since the hardening is brought about by further heating, after the initially plastic composition has been shaped and consolidated by pressure or heat and pressure.

In order to present disclosures possessing comparable significance, the .discussions herein refer to products made by mixing resin with hexa and wood flour (the proportion and kind of the latter being substantially similar in all compared cases) and heating such composite products under similar conditions of pressure and temperature. That is, the only variable in such cases is the proportion of hexa. Instead of wood flour,

other filling or extending material of cellular or fibrous character may be used, viz. ground corn cobs, cotton linters, cotton, wool or silk flock, asbestos; or amorphous or crystalline material such as mica, lampblack, rotten stone; and instead of ground or comminuted fillers, woven or felted fibers in sheet form may be used.

The following comparisons will illustrate the advantages .to be obtained by employing the novel proportions of hardening agent herein set forth:

Example 1.A substantially anhydrous solid brittle resin prepared from dextrose and phenol in which the proportion of combined or retained phenol to dextrose taken was approximately 950 to 445 was mixed with varying quantities of hexa and with wood flour and the product cured by heat and pressure until-it attained its maximum strength. The following data illustrates the effect of increasingproportions of hexa:

Maximumb 112i]!!- verse tea ng Per cent hexa men mpoundg persq. inch "reacted with a carbohydrate and a phenol in hydrate employed may be soluble or insoluble inwater, e. g., dextrose, dextrine, sucrose starch. A hexose or hexose yielding carbohydrate is preferred, particularly starch or dextrose.

As regards the phenol, ordinary phenol or car bolic acid is preferred,.although other phenolic bodies may be employed in some cases, e. g., the cresols and other homologues of phenol, naphthols, guaiacol, polyhydric phenols.

I also employa converting agent to assist in causing reaction. This is preferably an acidic substance of mineral origin, as for example, sulphuric or phosphoric acid.

This feature of the invention may be utilized as follows:

Example 2.--I-Ieat 960 grams of phenol and 13.6 grams of sulphuric acid (sp.. gr. 1.83-1.84) to about 130 degrees centigrade and gradually add 240 grams of China wood oil. Allow the solution to cool to about 120 degrees C. and add gradually 400 gramsvof Argo corn sugar (84 to 85 per cent dextrose, 4 to 5 percent dextrin and 10 to 11 per cent water and impurities). Apply heat and gradually distill these ingredients, in a vessel provided with an air cooled reflux condenser and a water cooled inclined condenser leading from the top of the reflux condenser. The distillate collected will comprise, in two layers, water containing phenol in solution, and a small amount of phenol containing water in solution. Most of the phenol used will, however, be retained in the reaction mixture by virtue of the reflux condenser. Continue heating and distillation until water ceases to be freely evolved. The temperature of the reactants may be carried to 180 degrees C.190 degrees C. It will be found that the total water evolved amounts toabout 211 grams and the total phenol distilled about 272 grams, corresponding to a retention or combination of 688 grams phenol. The carbohydrate employed contained 85 per cent dextrose and 4 per cent dextrin, or a total carbohydrate content of 89 per cent. The total carbohydrate present was 356 grams. 11 per cent, or 44 grams of moisture was present. The 688 grams of retained phenol is equivalent to 7.32 mols. If this amount condensed with the carbohydrate, 7.32 mols. of water or 131.76 grams ould be theoretically produced which, added to he 44 grams of water present in the carbohydrate, equals 175.76 grams. The amount of water actually obtained exceeds this quantity and ispalso greater than half the quantity of carbohydrate taken. Now, by further distillation, preferably assisted by a partial vacuum, re-

move-238 grams of phenol, maintaining a prope temperature, say 150 C.-180 C. i

The residue is liquid at temperatures not above 200 C., and at room temperature is solid, brittle, easily pulverizable, homogeneous, black in mass, brown or red in thin layers, soluble in alcohol, insoluble in water, partially soluble in sodium hydroxide solution, soluble in alcohol-acetone,

or alcohol-benzol mixtures, and not readily soluble in benzol, turpentine or gasoline. By heating to 230-2 60 C. it is changed from a liquid to a jelly-like consistency, i. e. it becomes infusible but not necessarily rigid. It is not soluble in ammonium hydroxide,butis decomposed by this reagent.

That the oil actually reacted with the carbohydrate, phenol and sulphuric acid under the conditions above described is indicated by the fact that the resulting resin can be dissolved in alcohol without a residue, whereas China wood oil is not compatible with or soluble in this solvent.

This 'resin possesses several advantages over the carbohydrate-phenol resins heretofore produced. -It possesses an increased resistance toward water and may be soaked in water without losing its gloss. After thorough incorporation with wood flour and hexa in any well known manner, the resulting molding compound possesses an increased plasticity or capacity to flow during hot-molding processes, even when the resin contains little or no free phenol.

It has the particular advantage that wood flour or molding compositions may be prepared therefrom which yield molded articles possessing an increased shock resistance or impact strength.

A binder mixture was made containing the resin prepared as above described and 20 per cent of its weight of hexa. This was mixed with substantially the same proportion of wood flour as used in molding mixtures hereinabove described under Example 1 and was subjected to the same heating and pressure conditions. The maximum impact strength of the resulting product was 1.12 foot pounds.

Another mixture was prepared differing from the above only in that 15 per cent of hexa was used instead of 20 per cent. The maximum impact strength of products of this mixture was 0.95 foot pound.

It is to be clearly understood that the proportions and kind of reacting substances may be varied within the scope of the claims without departing from the invention. This is particularly true with respect to.the fatty oil, fat or fatty acid, employed. By such variation the properties of the product may be changed. For example, by using larger proportions of oil, a softer, less brittle, and more diflicultly pulverized resin will be produced. Such a product may be less readily soluble in alcohol than the product described in the above example and may require a mixture of alcohol and benzol, or acetone and benzol, or other solvents, for its complete solution. A product of this character will possess still greater fluidity, or less viscosity, when heated and therefore be more particularly adapted for impregnating purposes.

For purposes where a high degree of resistance to impact (toughness) is required, I preferably employ the drying or 'semidrying oils; or fatty acids therefrom, e. g. linseed oil, China wood oil, perilla oil, corn oil, soya bean oil. Such oils are also preferably employed in cases where it is especially desirable that the resin be capable of .becoming infusible by heating without chemical hardening agents, as for example, in preparing mixtures for cold molding.

In some cases, the use of a less unsaturated, or even fully saturated oil, is desirable. cases, stearine may be used.

Whatever oil, fat, fatty pitch, or fatty acid is .used, it may be heated with a carbohydrate, a phenol and a converting agent, as described above in-connection with China wood oil, to yield a resin one or more improved properties (e. g., resistance to the action of water, fluidacid is produced when carbohydrates are heated In such ity when suitably heated, capacity to yield tough molded or pressed products).

To recapitulate, by employing more than 10 per cent of hexa with a carbohydrate phenol resin, I have been able to prepare molded wood flour products possessing greatly increased mechanical strength and toughness, more specifically, impact strength greater than 0.60 foot pound and a transverse breaking strength in excess of 9000 pounds per'sq. inch. This improvement may be enhanced by employing also a suitable fatty acid, as described.

The tests for transverse breaking strength used to determine the values disclosed herein were made according to the method described in the American Society for Testing Materials Standards, 1924, D 48-24, page 1063.

In testing for impact strength, a Charpy type machine was used with a capacity of 8 foot pounds. The specimens were rectangular unnotched bars, 5x "x The blow was struck parallel to the line of molding pressure and at a velocity of 11.3 feet per second. For further details concerning this test, see the 1926 Book of American Society for Testing Materials Tentative Standards, under the serial designation D 256-26T, and for more specific details see a paper by Werring in the Proceedings of the American Society for Testing Materials for 1926. ,Inasmuch as the results of such a test depend on the particular method used, the size and shape of specimen," and other details, a specific method must be employed in order that the results may be truly significant. The figures for impact strength described in the present specification and claims were obtained 'by pro-. ceeding according to the method referred to.

It is probable that the necessity for employing the novel and unusually large proportions of methylene hardening agent disclosed herein, in order to attain the high degree of mechanical strength and toughness described, is due to the capacity of the carbohydrate phenol resinsto react with the hardening agent for reasonsother than the presence of phenolic groups in the resins.

That is to say, it is probablethat an agent like hexa reacts not only with the phenolic portion of the resin but also with that portion which is derived from the carbohydrate.

i It is well known that humic 'acid and levulinic acid are formed by the action of mineral acids on carbohydrates.

It is quite likely that some humic or levulinic th phenols and acid catalysts and that such 11 c or levulinic acid forms a part of the re-' sulting .resins. Humic and levulinic acids react very readily with ammonia -(which is produced when hexa acts on phenol or phenolic bodies) and probably also with the methylene groups or formaldehyde yielded'by the hexa. It is highly probable that very considerable amounts of hexa can be used, with the advantages described, because of the reaction of the hexa, not only with the phenolic portion of the resin, but also with that portionconsisting of carbohydrate derivatives including humic and levulinic acid.

In the case of formaldehyde phenol resins, hexa is used to harden soft or fusible resins and in so doing merely supplies a quantity of formaldehyde in addition to that already present freely evolved when hexa acts on a formaldehyde phenol resin. It is mainly the formaldehyde of the hexa that reacts. Ammonia is not freely evolved when hexa acts on a carbohydrate phenol resin, according to my experience. Much of it is retained. The action of hexa on the car'oohydrate phenol resins appears to be quite difierent from its action on the well known formaldehyde phenol resins.

By the term hexamethylene tetramine, or hexa, I meanto include not only this specific substance, but also, any condensation product produced by the action on formaldehyde, or polymers thereof, of ammonia or aliphatic amines. Instead of hexamethylene tetramine, I may employ in some cases a hardening agent such as, for example, mixtures oi paraformaldehyde and ammonium carbonate, and also condensation products ,of formaldehyde (or other aldehyde) stearine pitch, candle pitch and palm oil pitch.

in a quantity sufllcient to combine with the other ingredients to form a resin of increased water resistance, impactstrength and transverse breaking strength. a

2. The process of claim 1 which includes heating with hexamethylenetetramine.

' JOSEPH V. MEIGS. 

